CN101760650B - Method for leaching vanadium in vanadium-containing stone coal by wet process - Google Patents
Method for leaching vanadium in vanadium-containing stone coal by wet process Download PDFInfo
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Abstract
The invention relates to a method for leaching vanadium in vanadium-containing stone coal by wet process. The method is characterized in that 98 percent of sulfuric acid is added into vanadium-containing stone coal, water is added to control the liquid-solid weight ratio, heating is carried out with the reaction temperature controlled between 70 DEG C to 100 DEG C, reaction lasts for 7 to 10 hours, and after liquid-solid separation, leachate is obtained; according to the total volume of the leachate, 30 percent to 70 percent of the leachate is taken out along with 98 percent of sulfuric acid, additional vanadium-containing stone coal is added, and the process is repeated; 10 percent of P204 and 5 percent of TBP which are diluted by kerosene are used to extract the leachate left each time, and sulfuric acid is used to strip the loaded organic phase; and after sodium chlorate is added in the stripped leachate, aqueous ammonia is added to regulate the pH value, precipitate is filtered, washed and calcined under the temperature of 550 DEG C, and thereby vanadium pentoxide is obtained. The method utilizes the residual acid in the leachate. The method has the advantages of high vanadium-leaching rate, less reagent consumption and little pollution. The method is applicable to the leaching of vanadium in vanadium-containing stone coal.
Description
Technical field
The present invention relates to a kind of scherbinaite coal wet-method for leaching that contains.
Background technology
China's bone coal reserves are quite abundant, claim according to southern bone coal resource comprehensive investigation report: province, autonomous region's bone coal total reservess such as Hunan, Hubei, Zhejiang, Jiangxi, Guangxi, Guizhou, Anhui, Henan, Shaanxi are 618.8 hundred million tons, 39.0 hundred million tons of proven reserve only contain V in the bone coal of Hunan, Hubei, Jiangxi, Zhejiang, Anhui, Guizhou, Shaanxi Qi Sheng
2O
5Just reach 1.1797 hundred million tons, wherein V
2O
5〉=0.5% reserves are 7707.5 ten thousand tons, are 6.7 times of vanadium reserves in China's vanadium titano-magnetite, are about the summation of countries in the world vanadium reserves.
China extracts the most employing of vanadium roasting and leaches from bone coal.On the one hand, owing to contain a certain amount of sulfide in the navajoite, the roasting meeting produces a large amount of SO
2, serious environment pollution; On the other hand, for the most of bone coal navajoite of China, the leaching yield of the vanadium of saltless roasting is lower.In order to improve the leaching yield of vanadium, need when roasting, to add sodium-chlor, but after adding sodium salt, can produce a large amount of HCl, Cl again in the roasting process
2Deng toxic gas, further environment is polluted.In order to solve environmental issue, the method that adopts direct strong acid to leach is proposed.Adopt direct pickling process, a large amount of SO that avoided roasting method in roasting process, to produce effectively
2, HCl and Cl
2Deng toxic gas.In general, the process cost of leaching process account for 30～50% of the total process cost of wet method vanadium extraction, and the sulfuric acid consumption that acid system leaches accounts for 70～80% of leaching expense again, and as seen, reducing the acid consumption is the important measures of extracting vanadium by stone coal wet method cost.Intensified acid soaking technology, sulfuric acid consumption increase, and make that residual acidity is too high in the leach liquor.In order to save cost, existing wet method process for extracting vanadium is all managed the spent acid that reuse produces.
Chinese patent application numbers 200810058171.4 discloses a kind of method that scherbinaite colliery and fluorite are produced Vanadium Pentoxide in FLAKES that contains.This method return the extraction and the washing after waste liquid, ammoniacal liquor deposition vanadium mother liquid and arsenic washing lotion, recycle a part of spent acid.Owing to regulate the pH value to 2.5 of leach liquor before the extraction with ammoniacal liquor, lost a large amount of acid, cause in the waste liquid of extraction back spent acid seldom.Equally, the spent acid in ammoniacal liquor deposition vanadium mother liquid and the arsenic washing lotion also seldom, it recycles leaching of vanadium influence little.
Also adopt " containing the surplus liquid round-robin test of vanadium leachate ion-exchange " that Fu Zibi etc. " steel vanadium titanium, 2009,30 (3): 21-25 " deliver ion exchange method to handle leach liquor, and recycle the leach liquor after the ion-exchange.Different be ion-exchange before, about the pH value to 7 with the NaOH regulator solution, most of spent acid is neutralized in the leach liquor, the just water that recycles, and ion exchange resin regeneration difficulty, cost is higher.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, propose a kind of wet-method for leaching that contains vanadium in the scherbinaite coal that utilizes the spent acid in the leach liquor.
Purpose of the present invention is achieved through the following technical solutions: be made up of following steps successively: it is broken, levigate to 100～200 orders that (1) will contain the scherbinaite coal dust, add 98% sulfuric acid that contains scherbinaite coal weight 8～35%, adding the water management solvent and solute weight ratio is 1: 1～2: 1, heating and control reaction temperature are 70～100 ℃, reaction 7～10h, liquid-solid separation obtains leach liquor; (2) by the leach liquor cumulative volume, take out 30～70%, with 98% sulfuric acid that contains scherbinaite coal weight 8～35%, add above-mentioned pulverizing, the levigated got in addition and contain the scherbinaite coal, (1) operation so repeats down set by step; (3) with the 10%P204 of kerosene dilution and 5%TBP as extraction agent, at room temperature, 7 grades of each remaining leach liquors of extraction are 7 grades of reextraction load organic phases of sulfuric acid of 1～4N with concentration; (4) in anti-stripping agent, add contain the sodium chlorate of scherbinaite coal weight 0.5～3.0% after, adding concentration and be 12% ammoniacal liquor, to regulate pH value be 2.2, filter, washing precipitation, 550 ℃ down calcining precipitate, obtain Vanadium Pentoxide in FLAKES.
Contain in the leach liquor of scherbinaite coal wet-method for leaching and contain spent acid, the sulfuric acid that spent acid in the round-robin leach liquor can and newly drop into reaches balance, the acid concentration of this moment is very high, can effectively leach the vanadium in the bone coal, particularly is present in vanadium in the mica with the isomorph form.
The present invention has following advantage: spent acid circulation to the leaching yield of the vanadium that is easy to extract greater than 90%; Still can reach more than 85% for the vanadium leaching yield that is difficult to extract that exists with the isomorph form.This method can also reduce the vitriolic consumption, saves sulfuric acid more than 20%, and simultaneously, after repeatedly circulating, the vanadium concentration in the leach liquor doubles approximately, has reduced the extraction cost.Because the minimizing of sulfuric acid consumption, also correspondingly reduced follow-up neutral ammonia volume, this has also reduced the cost that the whole wet method that contains vanadium in the scherbinaite coal leaches.This method vanadium leaching yield height, reagent consumption is few, pollutes few.
Embodiment
Below in conjunction with embodiment the present invention is further described.In the present invention, after leaching obtains leach liquor for the first time, by the leach liquor cumulative volume, getting 40%, 50%, 60% respectively leaches the scherbinaite coal that contains that other gets with 98% sulfuric acid that contains scherbinaite coal weight 8～35%, repeat 6-10 time, after the acid in the leach liquor, vanadium ion concentration and leaching yield keep stablizing, constantly repeat down, obtain the stable Vanadium Pentoxide in FLAKES of weight at every turn.
Embodiment 1
1. get the bone coal that 100g fragmentation, ball milling to 150 purpose contain vanadium 1.08%, drop in the reactor, add 25g 98% sulfuric acid, adding the water management solvent and solute weight ratio is 1: 1,70 ℃ of reaction 8h, filtration, washing precipitation obtain the 100ml leach liquor, measure pH value, vanadium ion concentration and the leaching yield of a leach liquor.
2. get 40ml leach liquor and 25g 98% sulfuric acid together, the 100g that other is got under with the condition of step 1 contains the scherbinaite coal and leaches, and so repetitive operation is gone down, and measures pH value, vanadium ion concentration and the leaching yield of each gained leach liquor.The results are shown in Table 1, after 6 repetitions, it is stable that the acid in the leach liquor, vanadium ion isoconcentration and leaching yield keep.
3. with the 100g 10%P204 and the 5%TBP extraction agent of kerosene dilution, at room temperature, 7 grades of 60ml leach liquors that extraction stays at every turn are the sulfuric acid of 2N with concentration, and 7 grades of reextraction load organic phases obtain anti-stripping agent 5ml; Add 2.5g sodium chlorate reaction 1h in anti-stripping agent, adding concentration again and be 12% ammoniacal liquor, to regulate pH value be 2.2, filter, 550 ℃ down calcining precipitate, obtain content and be 99% Vanadium Pentoxide in FLAKES.The results are shown in Table 1, the preceding Vanadium Pentoxide in FLAKES amount that obtains for 5 times is increasing always, and after repeating for 6 times, it is stable that the amount of Vanadium Pentoxide in FLAKES keeps, and can obtain about 1.311g at every turn.
Table 1 contains vanadium 1.08% bone coal circulation leaching experiment
Embodiment 2
1. get the bone coal that 100g fragmentation, ball milling to 100 purpose contain vanadium 0.993%, drop in the reactor, add 13g 98% sulfuric acid, adding the water management solvent and solute weight ratio is 2: 1,90 ℃ of reaction 10h, filtration, washing precipitation obtain the 200ml leach liquor, measure pH value, vanadium ion concentration and the leaching yield of a leach liquor.
2. get 100ml leach liquor and 13g 98% sulfuric acid together, the 100g that other is got under with the condition of step 1 contains the scherbinaite coal and leaches, and so repetitive operation is gone down, and measures pH value, vanadium ion concentration and the leaching yield of each gained leach liquor.The results are shown in Table 2, after 8 repetitions, it is stable that the acid in the leach liquor, vanadium ion isoconcentration and leaching yield keep.
3. with the 100g 10%P204 and the 5%TBP extraction agent of kerosene dilution, at room temperature, 7 grades of 100ml leach liquors that extraction stays at every turn are the sulfuric acid of 2N with concentration, and 7 grades of reextraction load organic phases obtain anti-stripping agent 5ml; Add 2g sodium chlorate reaction 1h in anti-stripping agent, adding concentration again and be 12% ammoniacal liquor, to regulate pH value be 2.2, filter, 550 ℃ down calcining precipitate, obtain content and be 99% Vanadium Pentoxide in FLAKES.The results are shown in Table 2, the preceding Vanadium Pentoxide in FLAKES amount that obtains for 7 times is increasing always, and after repeating for 8 times, it is stable that the amount of Vanadium Pentoxide in FLAKES keeps, and can obtain about 1.325g at every turn.
Table 2 contains vanadium 0.993% bone coal circulation leaching experiment
Embodiment 3
1. get the bone coal that 100g fragmentation, ball milling to 100 purpose contain vanadium 1.12%, drop in the reactor, add 20g 98% sulfuric acid, adding the water management solvent and solute weight ratio is 2: 1,80 ℃ of reaction 9h, filtration, washing precipitation obtain the 200ml leach liquor, measure pH value, vanadium ion concentration and the leaching yield of a leach liquor.
2. get 120ml leach liquor and 20g 98% sulfuric acid together, the 100g that other is got under with the condition of step 1 contains the scherbinaite coal and leaches, and so repetitive operation is gone down, and measures pH value, vanadium ion concentration and the leaching yield of each gained leach liquor.The results are shown in Table 3, after 10 repetitions, it is stable that the acid in the leach liquor, vanadium ion isoconcentration and leaching yield keep.
3. with the 100g 10%P204 and the 5%TBP extraction agent of kerosene dilution, at room temperature, 7 grades of 80ml leach liquors that extraction stays at every turn are the sulfuric acid of 3N with concentration, and 7 grades of reextraction load organic phases obtain anti-stripping agent 5ml; Add 1.5g sodium chlorate reaction 1h in anti-stripping agent, adding concentration again and be 12% ammoniacal liquor, to regulate pH value be 2.2, filter, 550 ℃ down calcining precipitate, obtain content and be 99% Vanadium Pentoxide in FLAKES.The results are shown in Table 2, the preceding Vanadium Pentoxide in FLAKES amount that obtains for 9 times is increasing always, and after repeating for 10 times, it is stable that the amount of Vanadium Pentoxide in FLAKES keeps, and can obtain about 1.394g at every turn.
Table 3 contains vanadium 1.12% bone coal circulation leaching experiment
Claims (2)
1. wet-method for leaching that contains vanadium in the scherbinaite coal, it is characterized in that being made up of following steps successively: it is broken, levigate to 100～200 orders that (1) will contain the scherbinaite coal dust, add 98% sulfuric acid that contains scherbinaite coal weight 8～35%, adding the water management solvent and solute weight ratio is 1: 1～2: 1, heating and control reaction temperature are 70～100 ℃, reaction 7～10h, liquid-solid separation obtains leach liquor; (2) by the leach liquor cumulative volume, take out 30～70%, with 98% sulfuric acid that contains scherbinaite coal weight 8～35%, add above-mentioned pulverizing, the levigated got in addition and contain the scherbinaite coal, (1) operation set by step, so repeat down, measure pH value, vanadium ion concentration and the leaching yield of each gained leach liquor, till the acid in leach liquor, vanadium ion concentration and leaching yield keep stablizing; (3) with the 10%P204 of kerosene dilution and 5%TBP as extraction agent, at room temperature, 7 grades of each remaining leach liquors of extraction are 7 grades of reextraction load organic phases of sulfuric acid of 1～4N with concentration; (4) in anti-stripping agent, add contain the sodium chlorate of scherbinaite coal weight 0.5～3.0% after, adding concentration and be 12% ammoniacal liquor, to regulate pH value be 2.2, filter, washing precipitation, 550 ℃ down calcining precipitate, obtain Vanadium Pentoxide in FLAKES.
2. the wet-method for leaching that contains vanadium in the scherbinaite coal according to claim 1 is characterized in that in the above-mentioned steps (2) that the multiplicity of (1) operation is 6～10 times set by step.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102251103A (en) * | 2011-05-27 | 2011-11-23 | 保靖天瑞钒业有限公司 | Circulating graded leaching method of stone coal acid-leaching vanadium extraction sulfuric acid |
| CN102212709A (en) * | 2011-06-15 | 2011-10-12 | 北京华夏建龙矿业科技有限公司 | Method for extracting vanadium by calcining vanadium-containing stone coal powder in calciner and pickling |
| CN102658234B (en) * | 2012-04-10 | 2015-03-25 | 西北有色地质研究院 | Application method of defoaming agent to beneficiation and tailings discarding of stone coal vanadium ore and hydrometallurgy |
| CN103374655B (en) * | 2012-04-24 | 2016-01-06 | 中国瑞林工程技术有限公司 | Wet method copper-extracting process |
| CN103290240A (en) * | 2013-07-02 | 2013-09-11 | 北京矿冶研究总院 | Method for extracting vanadium by utilizing sensible heat and low energy consumption of vanadium-containing stone coal power generation ash |
| CN106399684A (en) * | 2016-09-21 | 2017-02-15 | 武汉科技大学 | Solid-liquid separation method of leaching pulp of vanadium extraction from stone coal |
| CN109722533B (en) * | 2019-03-06 | 2020-09-01 | 吉首大学 | Method for preparing vanadium trioxide by using stone coal vanadium extraction pickle liquor |
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| CN101082085A (en) * | 2007-07-10 | 2007-12-05 | 刘健 | Method for vanadium leaching by sulfate-adding wet-pile oxidation conversion of stone coal under atmospheric temperature and atmosphere pressure |
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Effective date of registration: 20180208 Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Co-patentee after: Shaanxi Wuzhou Mining Co., Ltd. Patentee after: GUANGDONG INSTITUTE OF RARE METALS Address before: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Co-patentee before: Shaanxi Wuzhou Mining Co., Ltd. Patentee before: Guangzhou Research Institute of Non-ferrous Metals |
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Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of rare metals, Guangdong Academy of Sciences Patentee after: Shaoguan Yueyouyan Chemical Technology Co.,Ltd. Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: GUANGDONG INSTITUTE OF RARE METALS Patentee before: Shaoguan Yueyouyan Chemical Technology Co.,Ltd. |